# US 9,040,223 B2 · Resist composition, patterning process and polymer

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- Number: US 9,040,223 B2
- Document ID: US9040223B2
- Status: Granted
- Kind: B2
- Application number: 14/100,088
- Filed: 2013-12-09
- Published: 2014-06-26
- Granted: 2015-05-26
- Earliest claimed: 2012-12-26
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Jun Hatakeyama; Koji Hasegawa; Kenji Funatsu
- Web page: https://patentgrep.com/patent/US9040223B2

## CPC

- G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)}
- C08F 214/182: {Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28}
- C08F 214/186: {with non-fluorinated comonomers}
- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition}
- G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain}
- G03F 7/30: Imagewise removal using liquid means
- G03F 7/322: {Aqueous alkaline compositions}
- G03F 7/325: {Non-aqueous compositions}
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

An additive polymer comprising recurring styrene units having an ester group bonded to a CF3—C(OR2)—R3 group (wherein R2 is H, acyl or acid labile group, R3 is H, CH3 or CF3) such as 1,1,1,3,3,3-hexafluoro-2-propanol is added to a polymer capable of increasing alkali solubility under the action of acid to formulate a resist composition. The resist composition can minimize outgassing from a resist film during the EUV lithography and form a resist film having a hydrophilic surface sufficient to prevent formation of blob defects on the film after development.

## Claims

### Claim 1

A resist composition comprising a polymer capable of increasing alkali solubility under the action of acid as base resin, and a polymer comprising recurring units (p) of the general formula (1) as polymeric additive,
wherein R1 is a straight or branched C1-C4 alkylene group, R2 is C1-C15 acyl group or acid labile group, R3 is hydrogen, methyl or trifluoromethyl, and p is in the range:
0<p≦1.0.

### Claim 2 (depends on 1)

The resist composition of claim 1 wherein the additive polymer has the general formula (2):
wherein R1 to R3 are as defined above, R4 is hydrogen or methyl, X1 is a single bond, —C(═O)—O— or —O—, X2 and X3 each are phenylene or naphthylene, X4 is methylene, oxygen or sulfur, R5 is a C6-C20 aryl or aralkyl group which may contain a hydroxyl, straight, branched or cyclic alkyl or alkoxy, ester (—OCOR or —COOR wherein R is C1-C6 alkyl), ketone (—COR wherein R is C1-C6 alkyl), fluorine, trifluoromethyl, nitro, amino or cyano moiety, R6, R7, R8, and R9 are each independently hydrogen, hydroxyl, straight, branched or cyclic C1-C10 alkyl, alkoxy or acyloxy group, cyano, nitro, amino, halogen, ester (—OCOR or —COOR wherein R is C1-C6 alkyl or fluoroalkyl), or carboxyl group, v is 1 or 2, p, q1, q2, q3 and q4 are in the range: 0<p<1.0, 0≦q1<1.0, 0≦q2<1.0, 0≦q3<1.0, 0≦q4<1.0, and 0<q1+q2+q3+q4<1.0.

### Claim 3 (depends on 1)

The resist composition of claim 1 which is a chemically amplified positive resist composition.

### Claim 4 (depends on 3)

The resist composition of claim 3 wherein the polymer as base resin comprises recurring units having an acid labile group and recurring units having a hydroxyl and/or lactone ring adhesive group.

### Claim 5 (depends on 4)

The resist composition of claim 4 wherein the polymer as base resin has a weight average molecular weight of 1,000 to 500,000, and the recurring units having an acid labile group are recurring units of at least one type selected from recurring units (a1) and (a2) having a carboxyl and/or phenolic hydroxyl group substituted with an acid labile group, as represented by the general formula (3):
wherein R10 and R12 are each independently hydrogen or methyl, R11 and R13 each are an acid labile group, Y1 is a single bond, a C1-C12 linking group having at least one of ester (—COO—), lactone ring, phenylene and naphthylene, a phenylene group or a naphthylene group, Y2 is a single bond, ester (— COO—) group or amide (—CONH—) group, a1 and a2 are numbers in the range: 0≦a1≦0.9, 0≦a2≦0.9, and 0<a1+a2<1.0.

### Claim 6 (depends on 5)

The resist composition of claim 5 wherein the polymer comprising recurring units of at least one type selected from recurring units (a1) and (a2) having a carboxyl and/or phenolic hydroxyl group substituted with an acid labile group, represented by the general formula (3), has further copolymerized therein recurring units of at least one type selected from sulfonium salt units (b1) to (b3), as represented by the general formula (4):
wherein R020, R024, and R028 each are hydrogen or methyl, R021 is a single bond, phenylene, —O—R033—, or —C(═O)—Y—R033—, Y is oxygen or NH, R033 is a straight, branched or cyclic C1-C6 alkylene group, alkenylene group or phenylene group, which may contain a carbonyl, ester, ether, or hydroxyl moiety, R022, R023, R025, R026, R027, R029, R030, and R031 are each independently a straight, branched or cyclic C1-C12 alkyl group which may contain a carbonyl, ester or ether moiety, a C6-C12 aryl group, a C7-C20 aralkyl group, or a thiophenyl group, Z1 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—R032—, or —C(═O)—Z2—R032—, Z2 is oxygen or NH, R032 is a straight, branched or cyclic C1-C6 alkylene, alkenylene or phenylene group which may contain a carbonyl, ester, ether or hydroxyl moiety, M− is a non-nucleophilic counter ion, b1, b2 and b3 are in the range: 0≦b1≦0.3, 0≦b2≦0.3, 0≦b3≦0.3, and 0<b1+b2+b3≦0.3.

### Claim 7 (depends on 1)

The resist composition of claim 1, further comprising at least one of an organic solvent, basic compound, dissolution regulator, and surfactant.

### Claim 8 (depends on 1)

The resist composition of claim 1 wherein 0.1 to 50 parts by weight of the additive polymer is present per 100 parts by weight of the polymer as base resin.

### Claim 9 (depends on 1)

A pattern forming process comprising the steps of applying the resist composition of claim 1 onto a substrate to form a coating, baking, exposing the coating to high-energy radiation, and developing the exposed coating in a developer.

### Claim 10 (depends on 9)

The pattern forming process of claim 9 wherein the high-energy radiation is KrF excimer laser of wavelength 248 nm, ArF excimer laser of wavelength 193 nm, electron beam or soft x-ray of wavelength 3 to 15 nm.

### Claim 11

A polymer represented by the general formula (2) and having a weight average molecular weight of 1,000 to 500,000,
wherein R1 is a straight or branched C1-C4 alkylene group, R2 is C1-C15 acyl group or acid labile group, R3 is hydrogen, methyl or trifluoromethyl, R4 is hydrogen or methyl, X1 is a single bond, —C(═O)—O— or —O—, X2 and X3 each are phenylene or naphthylene, X4 is methylene, oxygen or sulfur, R5 is a C6-C20 aryl or aralkyl group which may contain a hydroxyl, straight, branched or cyclic alkyl or alkoxy, ester (—OCOR or —COOR wherein R is C1-C6 alkyl), ketone (—COR wherein R is C1-C6 alkyl), fluorine, trifluoromethyl, nitro, amino or cyano moiety, R6, R7, R8, and R9 are each independently hydrogen, hydroxyl, straight, branched or cyclic C1-C10 alkyl, alkoxy or acyloxy group, cyano, nitro, amino, halogen, ester (—OCOR or —COOR wherein R is C1-C6 alkyl or fluoroalkyl), or carboxyl group, v is 1 or 2, p, q1, q2, q3 and q4 are in the range: 0<p<1.0, 0≦q1<1.0, 0≦q2<1.0, 0≦q3<1.0, 0≦q4<1.0, and 0<q1+q2+q3+q4<1.0.